EP0110690A1 - Herstellung von Trifluormethylpyridinen - Google Patents

Herstellung von Trifluormethylpyridinen Download PDF

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Publication number
EP0110690A1
EP0110690A1 EP83307212A EP83307212A EP0110690A1 EP 0110690 A1 EP0110690 A1 EP 0110690A1 EP 83307212 A EP83307212 A EP 83307212A EP 83307212 A EP83307212 A EP 83307212A EP 0110690 A1 EP0110690 A1 EP 0110690A1
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EP
European Patent Office
Prior art keywords
pyridine
trifluoromethyl
reaction
trichloromethyl
dichloro
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP83307212A
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English (en)
French (fr)
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EP0110690B1 (de
Inventor
Alexander P. Fung
Charles A. Wilson
George S. Fujioka
John A. Werner
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Dow Chemical Co
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Dow Chemical Co
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Publication date
Priority claimed from US06/492,983 external-priority patent/US4650875A/en
Priority claimed from US06/520,399 external-priority patent/US4590279A/en
Application filed by Dow Chemical Co filed Critical Dow Chemical Co
Publication of EP0110690A1 publication Critical patent/EP0110690A1/de
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Publication of EP0110690B1 publication Critical patent/EP0110690B1/de
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Expired - Lifetime legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/61—Halogen atoms or nitro radicals

Definitions

  • the present invention relates to a method of preparing (trifluoromethyl)pyridine compounds by reacting (trichloromethyl)pyridine compounds with hydrogen fluoride in the presence of a catalytic amount of a metal halide or metal halide/phosphorus halide catalyst under liquid phase conditions.
  • Fluorination of (trichloromethyl)pyridine compounds has been carried out by vapor phase fluorination which requires the use of high temperatures.
  • Such vapor phase reactions suffer from disadvantages including, for example, energy costs associated with elevating the temperature of the reactants, the decomposition of starting materials and end products associated with high temperature vapor phase reaction systems and, furthermore, low conversion and/or low selectivities to the desired (trifluoromethyl)pyridine products.
  • a (trifluoromethyl)pyridine compound can be prepared in a liquid phase halogen (fluorine--chlorine) exchange reaction of an appropriate (trichloromethyl)pyridine compound.
  • the (trichloromethyl)-pyridine compound, containing one or two trichloromethyl groups, may optionally have substituents in other pyridine ring positions in addition to the trichloromethyl substituents.
  • the present method is conducted by contacting a (trichloromethyl)pyridine compound with hydrogen fluoride in the presence of a catalytic amount of a metal halide or a metal halide/phosphorus halide catalyst under liquid phase conditions sufficient to form the desired (trifluoromethyl)pyridine compound.
  • the present method provides a commercially efficient means of producing (trifluoromethyl)pyridine compounds in a liquid phase reaction system.
  • the liquid phase condition provides a reaction where the desired (trifluoromethyl)pyridine compounds are produced in a selective manner. Additionally, the present liquid phase reaction may be run continuously by the addition of starting materials to a reaction vessel while the desired (trifluoromethyl)pyridine product, which generally has a boiling point less than the temperature at which the reaction is conducted, is collected by the condensation of (trifluoromethyl)pyridine vapors.
  • a (trichloromethyl)pyridine compound is contacted with hydrogen fluoride and a catalytic amount of a metal halide or a metal halide/phosphorus halide catalyst, hereinafter referred to as "catalyst", under liquid phase reaction conditions, and, optionally, under superatmospheric pressure.
  • catalyst a metal halide or a metal halide/phosphorus halide catalyst
  • (Trichloromethyl)pyridine compounds employed as the starting material are unsubstituted or substituted-(trichloromethyl)pyridine compounds containing one or two trichloromethyl groups.
  • the trichloromethyl groups may be in a, p or y ring positions.
  • the pyridine ring optionally contains other substituents, besides the CC1 3 groups, which do not affect the halogen exchange reaction of this invention.
  • substituents include, for example, Cl, Br, I, or F.
  • Preferred (trichloromethyl)pyridine compounds include mono- or dichloro--p-trichloromethyl pyridine, such as, 2,3-dichloro-5--(trichloromethyl)pyridine; 2-chloro - 5-(trichloromethyl)pyridine; and 2,6-dichloro-3-(trichloromethyl)-pyridine.
  • Hydrogen fluoride is employed as the source of fluorine in the present reaction.
  • the hydrogen fluoride is introduced into the present reaction as hydrogen fluoride (anhydrous) or as hydrofluoric acid.
  • the hydrogen fluoride is bubbled into the reaction as a gas or fed into the reaction as a liquid.
  • Hydrogen fluoride (anhydrous) has a boiling point of 19.5°C and the liquid and gas consist of associated molecules.
  • Hydrogen fluoride (anhydrous) is a well-known compound and commercially available, generally in cylinders and tank cars. Hydrogen fluoride is also supplied as hydrofluoric acid which is hydrogen fluoride in aqueous solution.
  • hydrogen fluoride is contacted with the other reactants and preferably hydrogen fluoride (anhydrous) is employed as the hydrogen fluoride source.
  • Hydrogen fluoride is supplied at a ratio of at least 3 moles per mole of mono-(trichloromethyl)pyridine compound and preferably an excess of this amount is employed.
  • bis-(trichloromethyl)pyridine compounds are employed as starting materials at least 6 moles of HF per mole of bis-(trichloromethyl)pyridine compound are required to fluorinate the 2 trichloromethyl groups while it is preferred to supply an excess of this amount.
  • Suitable metal halides include metal chlorides and metal fluorides.
  • Suitable metal chlorides include FeCl 2 , FeCl 3 , NbCl,, TaCl . , WCl 6 , SnCl 4 , TiCl 4 or mixtures thereof.
  • Suitable metal fluorides include SbF 3 , FeF 2 , FeF 3 , AgF, KF, CrF 2 or mixtures thereof.
  • the metal halide catalysts are added to the present reaction in catalytic amounts, generally from 0.1 to 20 mole percent based on the amount of (trichloromethyl)pyridine compound starting material present, and preferably from about 0.5 to about 10 mole percent.
  • Preferred metal halide catalysts include FeCl 3 and FeF 3 .
  • Especially preferred metal halide catalysts are FeCl 2 , FeF 2 and mixtures thereof.
  • a metal halide/phosphorus halide combination is acceptable as a catalyst.
  • a metal halide/phosphorus halide combination is achieved by supplying a phosphorus halide to the reaction mixture in addition to the metal halide catalyst.
  • a preferred phosphorus halide is PC1 5 .
  • Catalysts bonded to inert supports or precursor compounds which form the catalysts in situ are also useful in the present invention.
  • inert supports to which the catalysts may be bonded include graphite, alumina, silica, silica alumina, various clays and molecular sieves which are all well known in the art.
  • the present reaction is conducted under liquid phase conditions at a temperature usually under 250°C, preferably at a temperature between 50°C and 190°C. It is especially preferred to conduct the present reaction at a temperature between 160°C and 180°C.
  • the present halogen exchange reaction is typically conducted in the presence of agitation sufficient to maintain an essentially homogenous mixture of the reactants.
  • the present reaction may advantageously be carried out at superatmospheric pressure in the range of from 5-1200 psig (135.8-8375.04 kP), but it is convenient to conduct the reaction at ambient atmospheric pressure. A most preferred pressure is about 15 psig (204.75 kP).
  • the order of addition of the reactants is not critical.
  • the (trichloromethyl)pyridine compound and the catalyst are admixed to form a reaction mixture and thereafter the hydrogen fluoride is added into this mixture, with stirring, until the reaction is completed, generally in from 1 to 100 hours.
  • the exact time that the reaction is complete will vary on a variety of factors, such as, temperature, catalyst concentration, HF flow rate, degree of agitation and pressure.
  • the hydrogen fluoride is fed into the reaction mixture as a liquid or, alternatively, may be bubbled or sparged into the reaction mixture as a gas.
  • 2,3-dichloro-5-(trichloromethyl)pyridine is mixed with a catalytic amount of FeCl 3 or FeCl 2 and then hydrogen fluoride (anhydrous) is continuously added into the reaction mixture while the temperature is increased to from 150°C to 190°C and preferably from 160°C to 180°C.
  • the reaction is usually completed in from 1 to 48 hours.
  • the hydrogen fluoride (anhydrous) and HC1 which escapes from the reaction mixture as vapor is conveniently collected employing conventional techniques such as by condensation.
  • a unique aspect of the present invention is presented when the desired (trifluoromethyl)pyridine compound which is being prepared has a boiling point below the temperature at which the reaction is conducted.
  • the (trifluoromethyl)pyridine product vaporizes as it is formed and is conveniently collected in a pure form, separate from any (trichloromethyl)pyridine starting materials which generally have boiling points greater than the temperature at which the reaction is conducted. This allows the reaction to be run continuously by the substantially continuous addition or feeding of (trichloromethyl)pyridine compound and hydrogen fluoride to the reaction mixture.
  • Example 4 Substantially the same procedure of Example 4 was carried out employing various catalysts under varying temperature and time conditions. The results are reported in Table 2.
  • Example 6 Substantially the same procedures of Example 6 were employed except 165 g of 3,4,5-trichloro-2-(trichloromethyl)pyridine and 9.82 g of FeCl 3 (11 mole %) was reacted with a molar excess of HF for 26 hours at 175°C and atmospheric pressure.
  • the product distribution in G.C. area % was as follows:
  • underfluorinated materials i.e., (chlorodifluoromethyl)-pyridines and (dichlorofluoromethyl)pyridines
  • chlorodifluoromethyl-pyridines and (dichlorofluoromethyl)pyridines are present in the reaction product mixture.
  • These underfluorinated materials are separated from the desired (trifluoromethyl)pyridine products, employing known separatory techniques, and recycled into the present fluorination reaction to form the desired (trifluoromethyl)pyridine products.
  • Over-fluorinated materials are also formed in the present reaction, i.e., fluoro-(trifluoromethyl)-pyridines or ring fluorinated pyridine compounds. These over-fluorinated materials are also readily separated from the desired (trifluoromethyl)pyridine product.
  • the over-fluorinated compounds are ring fluorinated pyridine compounds wherein the fluoro attached to the pyridine ring has displaced a chloro
  • the ring-fluoro is displaced by chloro by reacting the over-fluorinated product with a chlorinating agent, advantageously HC1, and optionally at superatmospheric pressures.
  • This reaction with HC1 or other chlorinating agent forms the desired chloro-(trifluoromethyl)pyridines from the over-fluorinated fluoro-(trifluoromethyl)-pyridine by-products.
  • the reaction with HC1 also forms chloro-(chlorodifluoromethyl)pyridines from an isomeric fluoro-(chlorodifluoromethyl)pyridine by-product. It is very desirable to reduce the amount of isomeric, i.e., fluoro-(chlorodifluoromethyl)pyridine, product because of the difficulty in separating it from the desired chloro-(trifluoromethyl)pyridine product.
  • the bomb was vented to a caustic scrubber and 2.5 g of a light tan liquid consisting of HF and 84.3% 2,3-dichloro-5--trifluoromethylpyridine (by wt.). This represents a 97.7% yield of 2,3-dichloro-5-trifluoromethylpyridine (by wt.) with 0.4% of 3-chloro-2-fluoro-5-trifluoromethylpyridine remaining. No additional products were observed by analysis with gas chromatography.
  • the resulting product contained 83.5 percent by weight 2,3-dichloro--5-(trifluoromethyl)pyridine, 11.8 percent by weight 3-chloro-2-fluoro-5-(trifluoromethyl)pyridine and the balance unidentified by-product.
  • Anhydrous HC1 gas was continuously sparged into the reaction mixture at a rate of about 25 ml/min throughout the reaction.
  • the temperature of the reaction mixture was kept between 140 and 160°C for 22.5 hours.
  • the reaction mixture was quenched with 100 ml of ice water.
  • the organic layer was separated, neutralized with NaHC0 3 and dried over Mgso 4 .
  • a 335 ml nickel vessel was charged with 105 g of a mixture containing 88 percent by weight 2,3-dichloro-5-(trifluoromethyl)pyridine and 12 percent by weight 3-chloro-2-fluoro-5-(chlorodifluoromethyl)-pyridine and 7 g of anhydrous FeCl 3 .
  • Anhydrous HC1 gas was continuously sparged into the reaction mixture at a rate of about 20 ml/min as the mixture was heated to a temperature of 170°C and maintained at this temperature for 7 hours.
  • the reaction mixture was quenched with 100 ml of ice water.
  • the organic layer was separated, washed twice with 100 ml of water, neutralized with NaHC0 3 and dried over MgSO 4 .
  • the initial composition of the mixture is indicated at time "0" in Table 4 in weight percent.
  • the final composition of the mixture is indicated in sample 9 in Table 4 after a 54 hour reaction period.
  • 3-chloro-2-fluoro-5-(trifluoromethyl)pyridine is prepared from 2,3-dichloro-5-(trichloromethyl)pyridine- employing the procedures described herein whereby the conditions are controlled to optimize the formation of the over-fluorinated product, i.e., 3-chloro-2--fluoro-5-(trifluoromethyl)pyridine.
  • This over--fluorinated product is useful as a starting material in the preparation of 3-fluoro-5-(trifluoromethyl)pyridinyl- oxy(or thio)phenoxy propionic acid and derivatives thereof which are exceptional herbicides.
  • Example 6 Substantially the same procedures of Example 6 were employed except that 143 g of 2,3-dichloro-5-(trifluoromethyl)pyridine (98% pure) and 4.37 g of FeCl 3 (5 mole %) was reacted with an excess molar amount of HF for 21 hours at 175°C and atmospheric pressure.
  • the product distribution in G.C. area % was as follows:
  • Example 6 Substantially the same procedures of Example 6 were repeated employing 180 g of 2,3-dichloro-5--(trichloromethyl)pyridine and 5 mole % (5.5 g) of FeCl 3 . The reaction was run for 55 hours. After 55 hours, the temperature of the reactants was decreased to 140°C and HC1 was bubbled into the reaction mixture at a rate of 25 ml/minute for 15 hours.
  • the product distribution in G.C. area was as follows:

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Pyridine Compounds (AREA)
EP83307212A 1982-11-26 1983-11-25 Herstellung von Trifluormethylpyridinen Expired - Lifetime EP0110690B1 (de)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
US44477382A 1982-11-26 1982-11-26
US444773 1982-11-26
US492983 1983-05-09
US06/492,983 US4650875A (en) 1983-05-09 1983-05-09 Preparation of (trifluoromethyl)pyridines
US06/520,399 US4590279A (en) 1982-11-26 1983-08-04 Preparation of (trifluoromethyl)pyridines under liquid phase conditions
US520399 1983-08-04

Publications (2)

Publication Number Publication Date
EP0110690A1 true EP0110690A1 (de) 1984-06-13
EP0110690B1 EP0110690B1 (de) 1990-09-26

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Application Number Title Priority Date Filing Date
EP83307212A Expired - Lifetime EP0110690B1 (de) 1982-11-26 1983-11-25 Herstellung von Trifluormethylpyridinen

Country Status (6)

Country Link
EP (1) EP0110690B1 (de)
AU (1) AU558120B2 (de)
BR (1) BR8306556A (de)
DE (1) DE3381907D1 (de)
DK (1) DK159421C (de)
IL (1) IL70307A (de)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0164104A2 (de) * 1984-06-08 1985-12-11 Dowelanco Herstellung von (Trifluormethyl)pyridinen
US4649201A (en) * 1985-12-27 1987-03-10 The Dow Chemical Company Removal of ferric chloride from halopyridines
EP0256146A1 (de) * 1982-04-16 1988-02-24 The Dow Chemical Company Katalysator-Wiederverwertung auf Flüssigkeitsphase-Halogen-Auswechslung
EP2213663A1 (de) * 2009-01-29 2010-08-04 Saltigo GmbH Herstellung von halogenierten N-heteroaromatischen Polyhalogenderivaten
WO2014198278A1 (en) * 2013-06-14 2014-12-18 Cheminova A/S A method for producing 2,3-dichloro-5-(trichloromethyl)pyridine
EP2831044A4 (de) * 2012-03-30 2015-11-11 Dow Agrosciences Llc Verfahren zur herstellung von 3-substituierte-6-trifluormethyl-pyridinen und verfahren zur verwendung halogenierter 6-trichloromethyl-pyridine
CN107954924A (zh) * 2016-10-18 2018-04-24 内蒙古佳瑞米精细化工有限公司 一种2-氟-3-氯-5-三氟甲基吡啶的制备方法
CN109232400A (zh) * 2018-11-22 2019-01-18 中触媒新材料股份有限公司 一种连续化合成2，3-二氯-5-三氟甲基吡啶的方法

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4629610A (en) * 1985-05-10 1986-12-16 Dow Chemical Co. Hydrogen fluoride recovery process

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2812607A1 (de) * 1977-10-21 1979-04-26 Ishihara Mining & Chemical Co 2-substituierte 5-trifluormethylpyridin-verbindungen und verfahren zu deren herstellung
US4266064A (en) * 1979-03-19 1981-05-05 Ishihara Sangyo Kaisha Ltd. Process for producing chloro β-trifluoromethylpyridines
EP0063872A1 (de) * 1981-04-27 1982-11-03 Imperial Chemical Industries Plc Verfahren zur Herstellung von Fluormethylpyridinen und bestimmte auf diese Weise erhaltene Verbindungen

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2862490D1 (en) * 1977-08-12 1988-04-21 Ici Plc Phenoxypyridine compound

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2812607A1 (de) * 1977-10-21 1979-04-26 Ishihara Mining & Chemical Co 2-substituierte 5-trifluormethylpyridin-verbindungen und verfahren zu deren herstellung
US4266064A (en) * 1979-03-19 1981-05-05 Ishihara Sangyo Kaisha Ltd. Process for producing chloro β-trifluoromethylpyridines
EP0063872A1 (de) * 1981-04-27 1982-11-03 Imperial Chemical Industries Plc Verfahren zur Herstellung von Fluormethylpyridinen und bestimmte auf diese Weise erhaltene Verbindungen

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0256146A1 (de) * 1982-04-16 1988-02-24 The Dow Chemical Company Katalysator-Wiederverwertung auf Flüssigkeitsphase-Halogen-Auswechslung
EP0164104A2 (de) * 1984-06-08 1985-12-11 Dowelanco Herstellung von (Trifluormethyl)pyridinen
EP0164104A3 (en) * 1984-06-08 1988-08-03 The Dow Chemical Company Preparation of (trifluoromethyl) pyridines
US4649201A (en) * 1985-12-27 1987-03-10 The Dow Chemical Company Removal of ferric chloride from halopyridines
EP2213663A1 (de) * 2009-01-29 2010-08-04 Saltigo GmbH Herstellung von halogenierten N-heteroaromatischen Polyhalogenderivaten
EP2831044A4 (de) * 2012-03-30 2015-11-11 Dow Agrosciences Llc Verfahren zur herstellung von 3-substituierte-6-trifluormethyl-pyridinen und verfahren zur verwendung halogenierter 6-trichloromethyl-pyridine
WO2014198278A1 (en) * 2013-06-14 2014-12-18 Cheminova A/S A method for producing 2,3-dichloro-5-(trichloromethyl)pyridine
CN105492425A (zh) * 2013-06-14 2016-04-13 切米诺瓦有限公司 用于生产2,3-二氯-5-(三氯甲基)吡啶的方法
US9809543B2 (en) 2013-06-14 2017-11-07 Cheminova A/S Method for producing 2,3-dichloro-5-(trichloromethyl)pyridine
CN105492425B (zh) * 2013-06-14 2018-03-27 切米诺瓦有限公司 用于生产2,3‑二氯‑5‑(三氯甲基)吡啶的方法
US10442765B2 (en) 2013-06-14 2019-10-15 Cheminova A/S Method for producing 2,3-dichloro-5-(trichloromethyl)pyridine
CN107954924A (zh) * 2016-10-18 2018-04-24 内蒙古佳瑞米精细化工有限公司 一种2-氟-3-氯-5-三氟甲基吡啶的制备方法
CN109232400A (zh) * 2018-11-22 2019-01-18 中触媒新材料股份有限公司 一种连续化合成2，3-二氯-5-三氟甲基吡啶的方法

Also Published As

Publication number Publication date
DK539883A (da) 1984-05-27
AU2169983A (en) 1984-05-31
IL70307A (en) 1987-02-27
DK539883D0 (da) 1983-11-25
EP0110690B1 (de) 1990-09-26
BR8306556A (pt) 1985-03-12
DE3381907D1 (de) 1990-10-31
AU558120B2 (en) 1987-01-22
DK159421B (da) 1990-10-15
DK159421C (da) 1991-04-08

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